The O-pyridyl phosphates and phosphorothioates were described by Rigterink in U.S. Pat. No. 3,244,586. Such compounds are particularly useful as insecticides and biocides. They are represented by Formula (I) ##STR1## wherein R represents halopyridyl, Z represents oxygen or sulfur and each R' independently represents lower alkyloxy, amino or lower alkylamino. Rigterink disclosed several methods for preparing the compounds but his preferred method comprised reacting a phosphorochloridate or phosphorochloridothioate of Formula (II) ##STR2## with an alkali metal or tertiary amine salt of a halopyridinol having the formula R--O-alkali metal or R--OH tertiary amine. The disclosed methods were carried out in an inert organic liquid under anhydrous conditions. In each of the disclosed processes an alkali metal chloride or the tertiary amine hydrochloride salt is produced as a reaction by-product which is removed by filtration. The disclosure of U.S. Pat. No. 3,244,586 is incorporated herein by reference.
Other phosphorothioates and phenylphosphonothioates have been similarly prepared and used. See, for example, the articles by O. Johnson in Chemical Week, pages 18-46 (26 July 1972) and by E. E. Kenaga and W. E. Allison in the Bulletin of the Entomological Society of America, Vol. 15, No. 2, pages 85-148 (June, 1969) which list many commercially available phosphorothioates and phenylphosphonothioates and which include U.S. patents pertaining to such compounds.
The phosphorothioates and phenylphosphonothioates referred to above and herein prepared correspond to the formulas ##STR3## wherein: R.sub.1 and R.sub.2 are each independently lower alkyl; and R is ##STR4## wherein: n is 0, 1, 2 or 3; and
X is nitro, cyano, halo (fluoro, chloro, bromo and iodo, inclusive), lower alkyl, lower alkoxy, lower alkylthio or lower alkylsulfinyl,
with the proviso that R does not bear more than one nitro group, lower alkylthio group or lower alkylsulfinyl group. By "lower alkyl" is meant in all instances alkyl of 1 to 4 carbon atoms (i.e. methyl, ethyl, propyl and butyl).
Compounds III-V are typically prepared by reacting (a) a compound corresponding to the formula EQU RO.sup..crclbar. M.sup..sym. (VI)
or EQU M.sup..sym..crclbar. O--C.sub.6 H.sub.4 --S--C.sub.6 H.sub.4 --O.sup..crclbar. M.sup..sym. (VII)
with (b) a compound corresponding to the formula ##STR5## wherein M is an alkali metal (e.g. Na, K, etc.) and R, R.sub.1 and R.sub.2 have the aforesaid meaning. This reaction is normally conducted in an inert organic liquid reaction medium under alkaline conditions.